7636 J . Org. Chem., Vol. 66, No. 23, 2001
Mateos et al.
(3H, s), 0.81 (3H, s), 0.94 (3H, s), 1.14 (3H, s), 2.17 (3H, s),
2.70 (1H, s), 2.92 (1H, s) ppm; 13C NMR (CDCl3) δ 14.4, 18.2,
22.0, 22.7, 22.8, 32.8 (2C), 36.3, 36.7, 39.4, 41.9, 45.1, 57.0,
60.0, 66.5, 210.0 ppm; MS EI m/z (relative intensity) 250 (M+,
3), 235 (4), 232 (6), 217 (8), 109 (100).
d, J ) 2.0 Hz), 2.85-3.10 (3H, m), 2.95 (1H, m), 5.60 (1H, d,
J ) 2.0 Hz), 7.20-7.40 (5H, m) ppm; 13C NMR (CDCl3) δ 18.0,
20.3, 21.6, 22.2, 24.1, 32.6, 33.3, 33.6, 39.5, 40.7, 44.7, 49.0,
49.9, 52.9, 68.5, 119.0, 126.9, 127.7 (2C), 128.5 (2C), 137.8,
147.3, 168.8, 216.2 ppm; MS EI m/z (relative intensity) 380
(M+, 9), 338 (9), 323 (3), 320 (9), 305 (6), 281 (36), 206 (100),
77 (31), 55 (63); HRMS EI 380.2364 (M+, C25H32O3), calcd
380.2351.
(E)-(3SR,4aRS,8aRS)-1-(3-Hydr oxy-2,5,5,8a-tetr am eth yl-
3,4,4a ,5,6,7,8,8a -octa h yd r on a p h th a len -1-yl)-3-p h en ylp r o-
p en on e (5). To a stirred solution of 4 (3.50 g, 14.0 mmol) in
EtOH (61 mL) were added gradually benzaldehyde (1.42 mL,
14.0 mmol) and NaOH (1.12 g, 28.0 mmol). The reaction
mixture was stirred at room temperature under argon for 24
h and then concentrated to afford a residue, which was
dissolved in H2O and extracted with Et2O. The combined
organic extracts were washed with brine. Removal of the
solvent afforded an orange crude, which was purified by flash
chromatography. Hexane/AcOEt (90/10) furnished 5 (3.50 g,
10.3 mmol, 74%) as a colorless solid: mp (t-BuOMe/hexane)
173-175 °C; IR ν 3412, 2926, 1605, 762 cm-1; 1H NMR (CDCl3)
δ 0.80-0.90 (8H, m), 0.84 (3H, s), 0.92 (3H, s), 1.18 (3H, s),
1.68 (3H, s), 2.55 (1H, m), 4.04 (1H, t, J ) 3.0 Hz), 6.74 (1H,
d, J ) 16 Hz), 7.47 (1H, d, J ) 16 Hz), 7.30-7.60 (5H, m) ppm;
13C NMR (CDCl3) δ 18.4, 18.7, 19.3, 21.6, 29.1, 32.7, 33.0, 37.3,
38.7, 41.7, 45.3, 69.1, 128.5 (2C), 128.7, 128.9 (3C), 130.5, 134.8,
145.4, 147.3, 200.9 ppm; MS EI m/z (relative intensity) 338
(M+, 5), 323 (5), 320 (7), 119 (100), 77 (28). Anal. Calcd for
Acet ic Acid (1RS,3SR,3a RS,5a RS,9a RS,9b RS)-1-H y-
d r oxy-3a ,6,6,9a -tetr a m eth yl-3-p h en yl-2,3,3a ,5a ,6,7,8,9,9a ,-
9b-decah ydr o-1H-cyclopen ta[a ]n aph th alen -4-yl Ester (9).
To a solution of 8 (2.80 g, 7.36 mmol) in MeOH (187 mL) at 0
°C was added NaBH4 (1.40 g, 36.8 mmol). The reaction mixture
was stirred at 0 °C under argon for 2 h and, after the addition
of acetone, concentrated. The residue was treated with brine
and Et2O, stirring for 30 min. The organic layer was separated,
and the aqueous phase was extracted with Et2O. The combined
organic extracts were washed with brine. Removal of the
solvent afforded 9 (2.59 g, 6.77 mmol, 92%) as a colorless oil:
IR ν 3503, 2926, 1744, 733, 700 cm-1; 1H NMR (CDCl3) δ 0.84
(3H, s), 0.94 (3H, s), 1.15 (3H, s), 1.31 (3H, s), 1.41 (3H, s),
1.80-2.00 (7H, m), 1.84 (1H, d, J ) 9.1 Hz), 2.16 (2H, dd, J 1
) 7.7 Hz, J 2 ) 8.7 Hz), 2.50 (1H, dt, J d ) 4.0 Hz, J t ) 12 Hz),
2.73 (1H, t, J ) 8.7 Hz), 2.94 (1H, d, J ) 2.0 Hz), 4.58 (1H,
m), 5.53 (1H, d, J ) 2.0 Hz), 7.10-7.40 (5H, m) ppm; 13C NMR
(CDCl3) δ 18.5, 20.5, 22.0, 24.8, 26.2, 33.1 (2C), 33.4, 38.7, 40.7,
40.9, 46.8, 51.6, 54.2, 61.6, 74.7, 119.6, 126.1, 126.1, 127.4 (2C),
129.0 (2C), 141.1, 147.2, 169.3 ppm; MS EI m/z (relative
intensity) 382 (M+, 3), 364 (5), 341 (8), 322 (24), 135 (100), 91
(78), 77 (35), 55 (97).
Tr ea tm en t of 9 w ith KOH (a q)/EtOH. To a solution of 9
(2.40 g, 6.27 mmol) in EtOH (18 mL) was added a 5 M aqueous
solution of KOH (2.5 mL). The mixture was stirred at room
temperature for 1 h and then concentrated under reduced
pressure. To the residue were added H2O and Et2O. The
organic layer was separated and the aqueous phase was
extracted with Et2O. The combined organic extracts were
washed with brine. Removal of the solvent afforded a 2/1
inseparable mixture of 10 and 11 (2.14 g, 6.27 mmol, 100%)
as a white solid.
C
23H30O2: C 81.61, H 8.93. Found: C 81.77, H 9.11.
(E)-(4a RS,8a RS)-3,4a ,8,8-Tetr a m eth yl-4-(3-p h en yla cr y-
loyl)-4a ,5,6,7,8,8a -h exa h yd r o-1H -n a p h t h a len -2-on e (6).
The same procedure used above to obtain 3 through oxidation
with PCC was applied to 5 (3.30 g, 9.75 mmol) yielding, after
45 min of reaction, 6 (3.12 g, 9.26 mmol, 95%) as a colorless
solid: mp (t-BuOMe/hexane) 129-131 °C; IR ν 2942, 1674,
1
1626, 764, 733 cm-1; H NMR (CDCl3) δ 0.80-1.70 (6H, m),
0.90 (3H, s), 0.92 (3H, s), 1.36 (3H, s), 1.64 (3H, s), 1.89 (1H,
dd, J 1 ) 5.1 Hz, J 2 ) 13 Hz), 2.46 (1H, dd, J 1 ) 13 Hz, J 2 ) 18
Hz), 2.59 (1H, dd, J 1 ) 5.1 Hz, J 2 ) 18 Hz), 6.75 (1H, d, J )
16 Hz), 7.36 (1H, d, J ) 16 Hz), 7.30-7.60 (5H, m) ppm; 13C
NMR (CDCl3) δ 12.7, 18.3, 19.1, 21.2, 32.5, 33.2, 35.4, 36.3,
39.6, 41.0, 50.7, 127.2, 128.6 (2C), 128.8, 129.1 (2C), 131.1,
134.1, 146.5, 164.0, 197.7, 200.0 ppm; MS EI m/z (relative
intensity) 336 (M+, 11), 321 (3), 131 (100), 77 (21). Anal. Calcd
for C23H28O2: C, 82.10; H, 8.39. Found: C, 81.98; H, 8.51.
Acetic Acid (3a SR,5a RS,9a RS,9bRS)-3a ,6,6,9a -Tetr a m -
eth yl-1-oxo-3-p h en yl-3a ,5a ,6,7,8,9,9a ,9b-octa h yd r o-1H-cy-
clop en ta [a ]n a p h th a len -4-yl Ester (7). Compound 6 (3.00
g, 8.92 mmol) was dissolved in a mixture of HClO4 (10-2 M)/
Ac2O (1 M)/AcOEt (300 mL). The solution was allowed to stand
at room temperature for 2 h. Saturated NaHCO3 was added
to quench the reaction. The organic layer was separated and
the aqueous phase was extracted with Et2O. The combined
organic extracts were washed with Na2CO3 (5%) and brine.
Removal of the solvent afforded a crude solid, which was
purified by flash chromatography. Hexane/Et2O (85/15) fur-
nished 7 (3.21 g, 8.47 mmol, 95%) as a colorless solid: mp (t-
BuOMe/hexane) 73-75 °C; IR ν 2926, 1763, 1694, 733, 702
cm-1; 1H NMR (CDCl3) δ 0.82 (6H, s), 1.20 (3H, s), 1.20-1.80
(5H, m), 1.50 (3H, s), 1.63 (3H, s), 1.87 (1H, d, J ) 2.4 Hz),
2.10 (1H, s), 2.59 (1H, dt, J d ) 4.9 Hz, J t ) 14 Hz), 5.44 (1H,
d, J ) 2.4 Hz), 5.96 (1H, s), 7.25-7.45 (5H, m) ppm; 13C NMR
(CDCl3) δ 17.9, 20.5, 22.0, 22.1, 22.6, 32.7, 33.0, 33.4, 40.6,
41.6, 47.7, 52.5, 67.5, 117.6, 127.6 (2C), 127.8 (2C), 128.6, 132.4,
136.1, 146.8, 168.8, 178.6, 207.4 ppm; MS EI m/z (relative
intensity) 378 (M+, 6), 335 (87), 172 (100), 77 (15), 55 (36).
Anal. Calcd for C25H30O3: C, 79.33; H, 7.99. Found: C, 79.17;
H, 8.08.
(1SR,3SR,3a RS,5a RS,9a RS,9bRS)-1-Hyd r oxy-3a ,6,6,9a -
t e t r a m e t h y l-3-p h e n y ld o d e c a h y d r o c y c lo p e n t a [a ]-
n a p h th a len -4-on e 10: 1H NMR (CDCl3) δ 0.84 (6H, s), 1.00-
1.90 (6H, m), 1.14 (3H, s), 1.47 (3H, s), 1.68 (1H, d, J ) 6.5
Hz), 2.00-2.60 (5H, m), 2.78 (1H, dd, J 1 ) 5.8 Hz, J 2 ) 13
Hz), 2.84 (1H, t, J ) 9.0 Hz), 4.65 (1H, m), 7.20-7.45 (5H, m)
ppm; 13C NMR (CDCl3) δ 18.7, 21.3, 24.0, 29.7, 32.8, 33.6, 35.4,
38.2, 38.7, 41.3, 41.5, 46.6, 55.6, 59.1, 66.1, 74.8, 126.3, 127.6
(2C), 129.8 (2C), 140.9, 216.0 ppm.
1
Hem ik eta l 11: H NMR (CDCl3) δ 0.86 (3H, s), 0.88 (3H,
s), 1.08 (3H, s), 1.31 (3H, s), 3.11 (1H, dd, J 1 ) 4.9 Hz, J 2 ) 11
Hz), 4.43 (1H, br s), 7.20-7.60 (5H, m) ppm.
(1SR,3SR,3a RS,6a RS,10a RS,10bSR)-1-Hyd r oxy-3a ,7,7,-
10a -tetr a m eth yl-3-p h en yld od eca h yd r o-4-oxa ben z[e]a zu -
len -5-on e (12). To a stirred solution of the inseparable mixture
10/11 (1.50 g, 4.41 mmol) in CH2Cl2 (33 mL) were added
NaHCO3 (37 mg, 0.44 mmol) and m-CPBA (840 mg, 4.87
mmol). The reaction mixture was stirred under argon at room
temperature for 3 days. Then, Na2SO3 (5%) was added, and
the resulting heterogeneous mixture was vigorously stirred for
1 h. The organic layer was separated, and the aqueous phase
was extracted with CH2Cl2. The combined organic extracts
were washed with Na2CO3 (5%) and brine. Removal of the
solvent afforded 12 (1.57 g, 4.41 mmol, 100%) as a white
solid: mp (CH2Cl2/hexane) 210-212 °C; IR ν 3576, 2926, 1717,
768, 708 cm-1; 1H NMR (CDCl3) δ 0.80-2.00 (9H, m), 0.90 (3H,
s), 1.05 (3H, s), 1.23 (3H, s), 1.34 (3H, s), 2.20-2.90 (4H, m),
3.02 (1H, dd, J 1 ) 11 Hz, J 2 ) 17 Hz), 5.10 (1H, ddd, J 1 ) 2.4
Hz, J 2 ) 5.5 Hz, J 3 ) 7.7 Hz), 7.20-7.50 (5H, m) ppm; 13C
NMR (CDCl3) δ 18.2 (2C), 21.8, 26.0, 33.1, 35.2, 35.7, 35.8,
39.8, 41.8, 44.9, 49.1, 56.1, 66.2, 80.1, 81.0, 127.2, 128.2 (2C),
129.8 (2C), 137.7, 174.7 ppm; MS EI m/z (relative intensity)
356 (M+, 7), 341 (5), 338 (2), 207 (100), 91 (34), 55 (26); HRMS
EI 356.2342 (M+, C23H32O3), calcd 356.2351. Anal. Calcd. for
Acetic Acid (3SR,3a RS,5a RS,9a RS,9bRS)-3a ,6,6,9a -Tet-
r am eth yl-1-oxo-3-ph en yl-2,3,3a,5a,6,7,8,9,9a,9b-decah ydr o-
1H-cyclop en ta [a ]n a p h th a len -4-yl Ester (8). To a solution
of 7 (3.10 g, 8.19 mmol) in AcOEt (25 mL) was added 10% Pd/C
(490 mg). The mixture was vigorously stirred at room tem-
perature under H2 atmosphere for 10 h. After removal of the
catalyst by filtration, the filtrate was concentrated to yield 8
(2.96 g, 7.78 mmol, 95%) as a colorless oil: IR ν 2926, 1757,
1
1734, 733, 702 cm-1; H NMR (CDCl3) δ 0.80-2.50 (6H, m),
0.83 (3H, s), 0.89 (3H, s), 1.17 (3H, s), 1.39 (6H, s), 1.80 (1H,
C23H32O3: C, 77.49; H 9.05. Found: C, 77.33; H, 8.97.